The synthesis of 1,2-dihydrocyclopenta (cd) fluoranthene

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Content THE SYNTHESIS OP 1, 2«DIHYDR0CYCL0PENTA( CD) FIB<BANTHENE A T h e sis P re se n te d to th e F a c u lty o f th e Departm ent o f Chem istry th e U n iv e rs ity o f S outhern C a lif o rn ia In P a r t i a l F u lfillm e n t o f th e B equirem ents f o r th e Degree M aster o f S cien ce in C hem istry by F ra n c is L . Chubb A p ril 1949 UM I Number: EP41570 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI EP41570 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 C Css<j This thesis, written by Fxanc.i&..L.*....Ciiu.'b.k • . ...................... ..... under the guidance of h .i.3 — Faculty Committee, and approved by all its members, has been presented to and accepted by the Council on Graduate Study and Research in partial fulfill ment of the requirements for the degree of ...Master..of.. Science . . . i n .Ghe^s trj. ............................................. i.I,.jS .* .B .a g a .r.d a .8 ,..................... Dean Date ...................... Faculty Committee Chairman Table o f Contents Page X* In tro d u c tio n X I I* D iscu ssio n 4 I I I * E xperim ental XI 17. Summary X ® B ib lio g rap h y X9 Acknowledgement The a u th o r i s in d eb ted t o Dr* M. C* K L oetael f o r h i s in v a lu a b le a s s is ta n c e and encouragem ent d u rin g t h i s in v e s tig a tio n * In tro d u c tio n The problem o f p re p a rin g compounds hav in g tw o-five-m em bered rin g s fu sed to th e o p p o site p e r i p o s itio n s o f n ap h th alen e has occupied th e a tte n tio n o f s e v e ra l in v e s tig a to r s . The evidence fo r and a g a in s t th e p o s s i b i l i t y o f p rep arin g compounds w ith such a s tr u c tu r e i s c o n f lic tin g . A ttem pts t o p rep are th e sim p le st p o s s ib le compound having t h i s s tr u c tu r e , l , 3-d ih y d ro c y clo p e n ta (fg )ae en a p h th en e ( I ) and some o f i t s d e r iv a tiv e s have been u n su ccessfu l* Mayer and Kaufmann* attem p ted to p re p a re th e hydrocarbon I by d i s t i l l i n g 5 -eth y lacen ap h th en e from z in c d u s t, b u t o b ta in e d o n ly acen ap h th y len e, F le is c h e r and Wolff** caused o x a ly l brom ide to r e a c t w ith aeenaphthene in th e p resen ce o f aluminum c h lo rid e in an attem p t to p rep are l,3 -d ik e to -l,2 * * d ih y d ro e y c lo p e n ta (fg )ae e n ap h th e n e ( I I ) , and o b ta in e d a compound, whose a n a ly s is d id n o t conform to s tr u c tu r e I I , F ie s e r and P eters® a ttem p ted to c y e liz e ^ -(5 -a c e n a p h th o y l)-^ $ - brom opropionic a c id by th e a c tio n o f aluminum c h lo rid e on th e f r e e a c id , b u t were u n s u c c e ss fu l; These r e s u l t s show th a t th e re i s c o n sid e ra b le r e s is ta n c e to th e c lo s in g o f a second five-m em bered p e ri r in g in th e naph th a le n e n u c le u s . The f a c t th a t 1 ,4 -an th rah y d ro q u in o n ed icarb o x y lic aeid form s o n ly a mono la c to n e i s f u r th e r evidence f o r th e r e s is ta n c e to th e c lo s in g o f sneh a r in g ; 4 ♦ F or nom enclature see Chemical A b s tra c ts . There i s some evid en ce to show th a t a s tr u c tu r e w ith two five-m em bered r in g s fu sed a c ro ss th e p e ri p o s itio n s o f th e n ap h th alen e n u c leu s can be form ed, sin c e two hydrocarbons a re known which supposedly c o n ta in t h i s s tru c tu re * They a re iso ru b ic e n e ( I I I ) and 5 , 6 ,1 1 ,12-diphenylenenaphthacene 5 (IV ). Iso ru b ice n e was f i r s t re p o rte d by C la r , who claim ed to have pre* p ared i t by h e a tin g benzene w ith 9,10*!-dichloro-9,10-dihydroanthraceiB - 9 , 1 0 - e n d o - ^ - s u c c i n i c an h y d rid e, in th e presen ce o f aluminum c h lo rid e . m 1 2 Fedorov6 has since reported the preparation o f isorubicene by heating 1 ,4 -d ic h lo ro -9 ,1 0 -d ih y d ro x y -9 , 1 0 -d ip h e n y l-9 ,1 0 -d ihyd ro an th racen e w ith sodium fo rm ate. T h is compound was d if f e r e n t from thec-one p rep ared by 7 ft C la r, D u fra isse and G irard * claim ed to have p rep ared 5 ,6 ,1 1 ,1 2 -d ip h e n y l- enenaphthacene by h e a tin g 5 ,ll-d ie h lo ro -6 ,1 2 -d ip h e n y ln a p h th a c e n e w ith p otassium h y d ro x id e. In view o f th e c o n f lic tin g evidence re g a rd in g th e e x is te n c e o f naph th a le n e d e r iv a tiv e s having two five-m em bered rin g s fu se d a c ro s s th e o p p o s ite p e ri p o s itio n s , i t appeared d e s ira b le to attem p t th e s y n th e s is o f such a compound by a new sequence which would leav e no doubt a s to th e n a tu re o f th e p o ly e y c lic s k e le to n . A ccordingly, an a ttem p t which proved 3 s u c c e s s fu l, was made to p rep are th e hydrocarbon, 1, 2-d ih y d ro c y c lo p e n ta (c d )- flu o ra n th e n e (V ). D iscu ssio n The hydrocarbon, lj2 * -d ih y d ro cy clo p en ta{ c d )flu o ran th en e (V) was sy n th e siz e d by th e sequence i l l u s t r a t e d in fo rm u las VI XI# 3-K eto- 1 , 2 ,3 ,lO b -te tra h y d ro flu o ra n th e n e (VI) v as caused to undergo th e (W C H iC O O fc t » z r >- S O W v v W « i PC > V » C H - C 6 6 «<- 0 ^ 6 VIIL * e > X I 5 Reform at sky R eactio n w ith e th y l b ro m o aeetate, to form e th y l 3 - ( 1 ,2 ,3 ,10b«* ts tra h y d r o flu o r a n th y lid e n e )- a c e ta te (V II), which was th e n s a p o n ifie d to form 3 - ( 1 ,2 ,3 ,lO b -te tra h y d ro flu o ra n th y lid e n e } « a c e t ic a c id ( V II I) . The a c id , V I II , was hydrogenated to form 3 - ( l , 2 ,3 , lO b -te tra h y d ro flu o ra n th y lJo - a c e tic a c id (IX ), F r i e d e l-C ra ft s in tra m o le c u la r a c y l a t ion o f which re s u lte d in th e fo rm atio n o f 1- k e t o - l , 2, 2a , 3 ,4 ,4 a-h ex ah y d ro c y clo p en ta (cd j- flu o ra n th e n e (X)* Clemmensen R eduction o f X r e s u lte d in th e fo rm atio n o f l,2 ,2 a ,3 ,4 ,4 a -h e x a h y d ro c y c lo p e n ta (c d )flu a ra n th e n e (X I), which y ie ld e d th e d e s ire d hydrocarbon 1 , 2-d ib y d ro c y c lo p e n ta { c d )flu o ra n th e n e (V) by de hydrogenation* The s t a r t i n g m a te ria l f o r t h i s in v e s tig a tio n , 3 - k e to - l,2 ,3 ,lO b - te tr a - h y d ro flu o ran th en e (V I), was f i r s t p rep are d by won Braun^® in 33$ y ie ld b y c y c liz a tio n o f - ( 9 -flu o ry l)~ p ro p io n y l c h lo rid e in petroleum e th e r in th e p resen ce o f aluminum ch lo rid e* When th e re a c tio n was e ffe c te d in n i t r o - q benzene, acco rd in g to th e pro ced u re used b y Baehmann and X lo e tz e l to c y c liz e 1 -p h en a n th ry lp ro p io n ic acid and 9 -p h e n a n th ry lp ro p io n ic a c id , a 77$ y ie ld o f th e ketone VI was obtained* Von Braun^® p rep ared - ( 9 - f l u o r y l )-p ro p io n ic a c id by cau sin g th e sodio d e riv a tiv e o f 9 -carb eth o x y flu o p en e to r e a c t w ith e th y l ^ -b ro m o - p ro p io n a te . The p o s s i b i l i t y o f p re p a rin g - ( 9 - f lu o r y l)-p ro p io n ic a c id by cau sin g e i t h e r flu o re n e o r 9 -c a rb e th o x y lflu o re n e to undergo th e M ichael C ondensation w ith a s u ita b le a c c e p to r such a s a e r y l o n i t r i l e o r e th y l a c r y la te was in v e s tig a te d . F lu o ren e i s known to undergo th e M ichael C ondensation, and t h i s r e a c tio n h as been used to p rep a re flu a ra n th e n e d e riv a tiv e s * F!rance, M aitlan d and T u c k e r^ have e f f e c te d th e condensa tio n o f flu o re n e w ith m e s ity l oxide to fozm 4 - ( 9 -flu o ry l)-4 * * m eth y l-2 -p en ta- none which was e y c liz e d to form 1, 1, 3- tr i m e t h y l - l , 10b ~ d ih y d ro flu o ran th en e and 1 , 1 , 3- tr i m e t h y l - l , 2, 3 , 10b - te tr a h y d r o f lu o ra n th e n e ^ • These compounds have been dehydrogenated t o 1 ,3 -d im eth y lflu o ra n th e n e and 1 , 2 , 3 -trim e th y l- flu o ra n th e n e ^ 3 * T ay lo r and C o n n o r^ have eaused flu o re n e t o condense w ith benzalaeetophenone, benzal-p-brom oaeetophenone, and b en zalacetone* P inch and H ilb e r t ^5 have eaused flu o re n e to condense w ith b e n z a lflu o re n e , d ib ip h en y le n e th y len e, 2 ,7 ,2 * ,7 * -te tra b ro m o d ib ip h e n y le n eth y len e and benzalaeetophenone* P in ck and H ilb e r t o b ta in e d th e same p ro d u ct a s T ay lo r and Connor from th e co n d en satio n o f flu o re n e w ith b en zalaeetophenone, b u t th e y su g g ested a d if f e r e n t s tru c tu re * T aylor and Connor su g g ested th e exp ected s tr u c tu r e X II, w h ile P in ck and H ilb e r t su g g ested th e s tr u c tu r e X III, sin c e th e y were unable to fin d any evidence th a t t h e i r p ro d u ct was a k e to n e i Bruson^6 e f fe c te d th e condensation o f flu o re n e w ith a c ry lo - n i t r i l e to foxm 9 - 9 - d i- ( -c y a n o e th y l)-flu o re n e and w ith e r o to n o n itr ile to f o r m - ( 9 - f lu o r y l ) « b u ty ro n itrile * X m When equim olar amounts o f flu o re n e and a e r y l o n i t r i l e w ere caused to 15 r e a c t, acco rd in g to th e pro ced u re used by P in ck and H ilb e r t to condense v > flu o re n e and b en zalaeeto p h en o n e, o n ly u n re ac te d flu o re n e and th e d isu b s t i t u t e d 9 ,9 -d i-(^ » -c y a n o e th y l)-flu o re n e were o b tain ed * However, 7 9 -carb eth o x y flu o re n e re a c te d w ith a e r y l o n i t r i l e to fozra 9 -e a rb e th o x y -9 - ( p -e y a n o o th y l)-flu o re n e i S a p o n ific a tio n and d ec a rb o x y la tio n o f th e l a t t e r y ie ld e d (9 - f lu o r y l)-p ro p io n ic a c id . I t i s e v id e n t th a t th e Michael Condensation between fluorene or su b stitu ted fluorene d erivativ es and s u ita b le a c c e p to rs should prove t o be a convenient method f o r th e pre*» p a ra tio n o f new flu o ra n th e n e d e r iv a tiv e s . The k eto n ej 3-keto**l, 2 ,3 , lO b -te tra h y d ro flu o ra n th e n e was s u b je c te d to the Reformat sky Reaction with eth y l bromoacetate according to the procedure 17 u sed by Bachmann and E dgerton on 4- k e t o - l , 2 , 3 ,4 -te tra h y d ro p h e n a n th re n e , and a 91% y ie ld o f a yellow o i l was o b ta in e d ; T h is yellow o i l proved to be a m ix tu re o f e s t e r s . Two s o lid e s te r s were is o la te d from th e m ix tu re . A n a ly sis showed t h a t one o f th e s e was th e expected e s te r , e th y l 3 - ( 1 ,2 ,5 ,10b- te tra h y d ro f lu o ra n th y lid e n e ) -a c e ta te (V II) o r i t s isom er (XI7}t and th a t th e o th e r was e th y l 3 -flu o r a n th y la c e ta te (XV) • When th e e s te r m ix tu re was + C w - 1 TV T dehydrogenated by h e a tin g w ith a p a lla d iu m -o n -c h a re o a l c a ta ly s t, a 90% y ie ld o f e th y l 3 -flu o r a n th y la e e ta te was o b ta in e d , and t h i s p ro d u ct proved to be id e n tic a l w ith th e e th y l 3 * flu o ra n th y la e e ta te is o la te d d i r e c t l y from th e Reform at sky R e a c tio n . I t i s p o s s ib le f o r th e u n s a tu ra te d e s t e r t o e x is t in th re e iso m eric form s, XXV, XVII,,3SVIIIi one w ith th e double bond in th e z in g (XIV); and I x t ^ th e e i s and tr a n s isom ers, w ith th e double bond co n ju g ated w ith th e e s te r group ( X 7 I I ) ( X m i) . E th y l 3 -flu o r a n th y la c e ta te was p ro b ab ly formed by d is p ro p o rtio n a tlo n o f one o f th e u n s a tu ra te d e s te r s a s shown in ( l ) f and co n seq u en tly th e s a tu r a te d e s t e r , e th y l 3 - ( 1 ,2 ,3 ,lO b -te t ra h y d ro f lu o ra n th y l )« ■ a e e ta te (XVI), may a ls o be p re se n t* E th y l 3 - ( 1 ,2 ,3 ,lO b -te tra h y d ro flu o ra n th y l) a c e ta te has two asym m etric aarbon atoms and may e x is t a s two raeem ic mix tu re s * S in ce th e two e s t e r s which have th u s f a r been is o la te d o n ly account f o r p a r t o f th e m ixture* some o r a l l o f th e o th e r fo u r p o s s ib le iso m eric compounds may be p re se n t* The e s t e r m ix tu re was s a p o n ifie d and th e r e s u ltin g m ix tu re o f a c id s was hydrogenated c a t a l y t i c a l l y , u s in g Adams* C a ta ly st* One o f th e racem ic 3 - ( l,2 ,3 ,1 0 b -te tr a h y d ro f lu o rs o ith y l)- a c e tic a c id s was o b ta in e d in 47# y ie ld . T h is y ie ld was low er th an ex p ected sin e e an amount o f hydrogen app ro x im ately corresp o n d in g to Q onplete re d u c tio n o f th e ac id was ta k e n up* A second a c id was is o la te d from th e resid u e* and a n a ly s is in d ic a te d i t was th e isom er o f IX* A s o lid re s id u e , p ro b ab ly a m ix tu re o f th e isom ers o f IX, remained* The a c id IX was o y c liz e d b y th e same method used to e y c liz e ^ - ( 9 - f lu o r y l) - p r o p io n ic a c id and a 61# y ie ld o f l-k e to -l* 2 ,2 a * 3 * 4 ,4 a - h e x ah y d ro cy clo p en ta(c d )flu o ran th en e was obtained* The s u c c e s s fu l s y n th e s is \ X V t t o f t h i s ketone shows th a t a second five-m em bered rin g can be c y c liz e d a c ro s s th e o p p o site p e r i p o s itio n s o f th e n ap h th alen e n u c le u s, p ro v id ed th e r in g to which th e s id e ch ain i s a tta c h e d i s s a tu r a te d . When 3 - f lu o r s n th y la e e tic a c id , p rep ared by th e s a p o n ific a tio n o f e th y l 3 - flu o r a n th y la c e ta te (XV), was s u b je c te d to th e F r ie d e l C ra fts in tra m o le c u la r a c y la tio n r e a c tio n , an In so lu b le yellow powder, p ro b ab ly a polym er, was o b ta in e d . T his r e s u l t i s in conform ity w ith th e f a i lu r e o f a l l o th e r re p o rte d a tte m p ts to c y c liz e a second five-m em bered r in g a c ro s s th e p e r i p o s itio n s o f a f u l l y aro m atic n ap h th alen e n u c le u s . S ince a l l th e s e u n s u c c e ssfu l a tte m p ts have in v o lv ed th e u se o f aeenaphthene o r one o f i t s d e r iv a tiv e s a s th e s t a r t i n g m a te r ia l, where b o th th e n ap h th alen e rin g s a re aro m atic , th e f a i l u r e o f th e s e a tte m p ts may be due to s t r a i n in th e aeenaphthene m olecule* N aphthalene i s known A IQ to have a p la n a r s tr u c tu r e w ith 120 bond a n g l e s '. I f th e n ap h th alen e bond a n g le s rem ain u n s tra in e d when a five-m em bered r in g i s fu sed a c ro s s th e p e r i p o s itio n s o f n ap h th alen e a s in aeenaphthene, th en one o f th e bond o a n g le s in th e five-m em bered r in g would be 120 * T h is means th a t a s tr a i n o f 12° must be d i s tr ib u te d among th e o th e r a n g le s sin c e 108° i s th e norm al bond an g le f o r a five-m em bered r in g . However, th e s t r a i n i s p ro b ab ly d is t r ib u te d over th e w hole aeenaphthene m o lecule, and m ight r e s u l t in a s li g h t in c re a s e in th e d is ta n c e betw een th e two p e r i carbon atoms in aeenaphthene a s compared w ith th e co rresp o n d in g carbon atom s in nap h th alen e* T his m ight account f o r th e d i f f i c u l t y in c y c liz in g a second five-m em bered r in g a e ro s s th e p e r i p o s itio n s o f a n ap h th alen e n u c le u s . The f a c t th a t acenaph- 19 thenone can be p rep are d by th e e y c liz a tio n o f ^ - n a p h th y la c e tic a c id m ight be co n sid ered ev id en ce in su p p o rt o f t h i s idea* o o JT * •? o O' \t>t» tvo l*to \ 1 0 ‘ ‘■ to *oo 1V O \H o ito **© The hydrocarbon, 1 ,2 ,2 a ,3 ,4 ,4 a -h ex ah y d ro c y clo p en ta (cd )flu o ran th en e (XI) was p rep ared by Clemmensen re d u c tio n o f th e k eto n e X. When th e hydrocarbon XI was h e a te d w ith p allad iu m on c h a rc o a l c a ta ly s t a volume o f hydrogen e q u iv a le n t to two m oles p e r mole o f hydrocarbon was evolved, and th e f in a l p ro d u c t, 1 , 3 -d ih y d ro e y c lo p e n ta (c d )flu o ra n th e n e was o b ta in e d . A com parison o f th e u l t r a v i o l e t a b so rp tio n spectrum o f l,2 -d ih y d ro c y d © p e n ta (c d )- flu o ra n th e n e w ith t h a t o f flu o ra n th e n e 20 (F ig i 1) shows a g e n e ra l s im il a r i t y , b u t w ith a s li g h t s h i f t tow ard th e v i s i b l e re g io n in th e case o f th e form er hydrocarboni A rearrangem ent o f th e p o ly c y e lic sk e le to n to th e s tr u c tu r e XIX d u rin g dehydrogenation would n o t be exp ected , sin c e 1 , 9 -c y clo h ex y len eflu o ren e (XX) upon dehydrogenation form s 9 -p h e n y lflu o re n e 2! ; The s u c c e s s fu l s y n th e s is o f 1 , 2-d ih y d ro c y c lo p e n ta ( cd)flu o ra n th e n e , which h as two five-m em bered r in g s fu sed to th e o p p o site p e r i p o s itio n s o f a f u l l y aro m atic n ap h th alen e n u c le u s, shows th a t such a s tr u c tu r e once fonned i s s ta b l e . The method o f s y n th e s is h e re in re p o rte d should be a p p lic a b le to th e s y n th e s is o f o th e r compounds o f a s im ila r s tr u c tu r e . While th e s y n th e s is o f 1 ,2 -d ih y d ro c y c lo p e n ta (c d )flu o ra n th e n e does n o t oonfirm th e s tr u c tu r e s giv en f o r iso ru b ic e n e ( I I I ) and 5 ,6 ,1 1 ,1 2 -d i- phenylenenaphthaeene (IV ), i t does in d ic a te th a t such s tr u c tu r e s may be capable o f e x is ta n c e . E xperim ental C ondensation, o f F luorene and A e r y lo n itr ile . Ten g* o f flu o re n e and 3 .2 g . o f a e r y l o n i t r i l e w ere s u b je c te d to th e M ichael C ondensation a cc o rd in g to th e procedure used by P inck and H ilb e r t f o r flu o re n e and benzalaeetophenone# A f te r sta n d in g f o r tw e n ty -e ig h t days a t room tem p eratu re th e m ix tu re was d ilu te d w ith 400 ml# w a te r, a c id if ie d , f i l t e r e d and d r ie d . B e e r y s ta lliz a tio n from e th a n o l y ie ld e d 5 g# o f un re a c te d flu o re n e # The re s id u e was b o ile d f o r f iv e h o u rs w ith 20# potassium hydroxide# A c id if ic a tio n o f th e a lk a lin e s o lu tio n gave a p r e c i p i ta te o f 9 , 9 -d i-(^ -e a rb o x y e th y l)* » flu o re n e , i& ich was r e c r y s t a l l i z e d from a c e tic a c id to y ie ld 1#3 g . o f c o lo r le s s c r y s ta ls , m#p# 270-3°# Bruson r e p o rte d a m.p# o f 273-4° f o r t h i s compound*®# M ichael C ondensation of. A e r y lo n itr ile and 9 -G arb eth o x y flu o ren e# To a s o lu tio n o f 14.25 g# o f 9 -c a rb e th o x y flu o re n e 22 and 3 .2 g# o f a e r y l o n i t r i l e in 25 ml# o f p y rid in e was added 5 m l. o f 50# sodium hydroxide s o lu tio n . The m ix tu re was shaken and th e r e a c tio n began im m ediately w ith th e e v o lu tio n o f h e a t. A f te r co o lin g th e m ixture and allo w in g i t to s ta n d f o r o n e -h a lf h o u r, i t was d ilu te d w ith 300 ml# o f w a te r, made a c id w ith c o n c e n tra te d h y d ro c h lo ric a c id and th e a rg a n ie la y e r was ta k e n up in b en zen e. The benzene la y e r was washed w ith d i l u t e h y d ro c h lo ric a c id and w ater, th e benzene was ev ap o rated o f f and th e product was d i s t i l l e d under reduced p re ssu re # A y ie ld o f 16#4 g# (94#) o f 9-carbethyoxy-9(J& -cy an o - e th y l)-flu o re n e # b.p# 210- 20° a t 1 -2 m m # p re ss u re , was ob tain ed # 12 H y d ro ly sis and D ecarb o x y latio n o f 9 -C arb eth o x y -9 -( ««cyanoe t h y l)- f lu o r e n e . A m ix tu re o f 16.4 g . o f 9 -c a rb eth o x y -9 - -c y a n o e th y l)- flu o rene and 200 m l. o f 20^5 po tassiu m hydroxide was b o ile d f o r fo u r h o u rs, d ilu te d w ith w ater, a c id if ie d w ith h y d ro c h lo ric a c id , and th e p r e c ip ita te o f crude d i b a s ic a c id was f i l t e r e d and d ried # The p r e c i p i ta te was h e a te d to 250° and when e v o lu tio n o f carbon d io x id e ceased i t was cooled and r e c r y s t a l liz e d from benzene and h e p ta n e . A y ie ld o f 1 2 .8 g* (95$) o f c r y s ta ls o f (S - ( 9 - f lu o r y l) - p r o p io n ic a c id , m.p* 141-5°, was o b ta in e d . Two recrystal*» l i z a t i o n s from a c e tic a c id and w a te r r a is e d th e m .p . to 146^8°. A mixed m e ltin g p o in t d e te rm in a tio n w ith an a u th e n tic sample p rep ared from th e sodio d e riv a tiv e o f 9-earbethoxyfluoresne and e t h y l p «*bromopropionate showed no d ep re ssio n o f m .p. O y c liz a tio n o f - ( 9 - f lu o r y l) - p r o p io n ic A cid. F o rty grams o f |l-(9 * * flu o ry l)-p ro p io n ic a c id was e y d lz e d acco rd in g 9 to t h e method used by Bachmann and K Loetzel t o c y d i z e 1-p h e n a n th y l- p ro p io n ic a c id and 9 -p h en an th y lp ro p io n ic a c id . The a c id was warmed g e n tly w ith 68 m l. o f th io n y l c h lo rid e on a steam b ath f o r f i f t e e n m in u tes. The ex cess th io n y l c h lo rid e was removed by d i s t i l l a t i o n u nder reduced p re s s u re , th e a c id c h lo rid e was d iss o lv e d in 80 m l. o f n itro b e n z e n e and slow ly added to an ic e c o ld s o lu tio n o f 40 g . o f aluminum c h lo rid e in 320 m l. o f nitro<* b en zen e. A fte r s t i r r i n g th e m ix tu re a t 0° f o r fo u r h o u rs, i t was hydro ly se d w ith 200 g . o f ic e and 60 m l. o f c o n c e n tra te d h y d ro c h lo ric a c id and th e n itro b e n z e n e was removed by steam d i s t i l l a t i o n . The s o lid re s id u e was d isso lv e d in benzene, e x tr a c te d w ith 10% sodium carb o n ate s o lu tio n , washed w ith w a te r and th e so lv e n t was d i s t i l l e d o f f . D i s t i l l a t i o n o f th e s o lid k eto n e, 3 - k e t o - l , 2, 3 , lO b -te tra h y d ro flu o ra n th e n e (V I), y ie ld e d 28;5 g« (77%) o f c r y s ta ls , b .p . 180-90° a t 3 -3 m m * p re s s u re , m.p* 99-100°* Von Braun r e p o rte d a m .p. o f 98° f o r t h i s compound^0 . Refonaatsky R eactio n o f 3 - K e to -l.2 . 3 . lO b -te tra h y d ro flu o ra n th e n e w ith E th y l Brombacetate (V I)« T w enty-four grama p t 3 - k e t o - l ,2 ,3 ,lO b -te tra h y d ro flu o ra n th e n e was s u b je c te d to th e R efonaatsky R ea c tio n acco rd in g to th e p ro ced u re u sed by Bachmann and E dgerton *7 on 4 « * k e to -l,2 ,3 ,4 rte tra h y d ro p h e n a n th re n e . E th y l b ro m o aeetate was used in s te a d o f m ethyl b ram o aeetate, and th e crude h y d ro z y e ste r was dehydrated by h e a tin g to 200° u n d er 1 -2 mm. p r e s s u re . The p ro d u ct was d i s t i l l e d , y ie ld in g 29 g . (91%) o f a p a le yellow o i l , b .p . 210-20° a t 1-2 m m * A fte r sta n d in g f o r s e v e ra l days th e o i l slo w ly c r y s t a l l i z e d . F r a c tio n a l c r y s t a l l i z a t i o n from p etroleum e th e r and h ep tan e y ie ld e d two crops o f c r y s t a l s ; The f i r s t crop, e th y l 3?>fluoran- th y la c e ta te , c r y s ta lliz e d in p a le yellow p la te s from a lc o h o l, m .p; 111- 2° , showed th e c h a r a c t e r is t i c b lu e -g re e n flu o re s c e n c e o f flu o ra n th e n e d e riv a t i v e s . A nal. C aled . f o r ^20^10^2* 8 3 .3 4 ; H, 5 .5 9 . Founds 0, 83.07} H, 5.70 The second crop c r y s ta lliz e d in c o lo r le s s n e e d le s from a lc o h o l, m .p. » . - t 111-2°, and a n a ly sis showed i t was eth yl 3 - ( l , 2 }3 ,lOb-tetrahydrofluoran- th y lid en e)-a ceta te or an isomer. A nal, C alcd ; f o r O 2oH 10Og : G, 8 2 .7 6 ; H, 6*25, Found: C, S 2;69; H, 6.47 S a p o n ific a tio n o f th e E s te r M ixture from th e Reform at sky R e a c tio n * The m ix tu re o f e s te r s from th e B eforraatsky B eactio n was s a p o n ifie d by b o ilin g w ith 20$ sodium hydroxide s o lu tio n f o r f i f t e e n m in u tes. The a e id s were p r e c ip ita te d by adding h y d ro c h lo ric a c id to th e s o lu tio n , f i l t e r e d and re c r y s ta lliz e d from a c e tie a c id and w atery A y ie ld o f 85$ o f mixed a e id isom ers o f 3 - (1 * 2 ,3 , lO b -te t ra h y d ro flu o ra n th ry lid e n e ) - a c e tic a c id , o m .p. 180-6 , s u ita b le f o r re d u c tio n , was o b ta in e d . P re p a ra tio n o f 5 - ( l,2 ,5 .1 0 b - te tr a h y d r o f lu o r a ith y l) - a c e tio A cid (IX ). Twenty grams o f th e a c id m ix tu re from th e a fo re d e s c rib e d s a p o n ific a tio n was hydrogenated in th e p resen ce o f 4 mg* o f Adams* C a ta ly s t in 200 m l. o f g la c i a l a c e tic a e id . The hydrogen p re ssu re dropped from 31 to 23 l b s . in th r e e h o u rs . C r y s ta lliz a tio n o f th e p ro d u et from g l a c i a l a c e tie a c id gave 9 .5 g; (47$) o f 3 - ( l , 2 , 3 f 1 0 b -te tra h y d ro flu o ra n th y l} * a c e tic a c id (IX ), m .p. 1 5 1 -5 °. A sample r e c r y s ta lliz e d fo u r tim es from g l a e i a l a c e tic a c id y ie ld e d c o lo r le s s n e e d le s , m.p* 1 5 7 -8 °. A nal. C aled , f o r C H O ; c, 81.80; H, 6.11. Pound: C, 81.69; H, 5.91 18 2 Re c r y s ta l l i z a t i o n o f th e re sid u e from a lc o h o l y ie ld e d a sm all q u a n tity o f a second a c id , which formed c o lo r le s s n e e d le s , m .p; 1 7 8 -9 °. A n al. C aled. f o r C1Q H 160 2 : C, 8 1.80; H, 6*11; Pound: C, 8 2 .2 6 ; H, 6.59 A s o lid re s id u e , p ro b ab ly a m ix tu re o f th e two a c id s , was l e f t o v e r; C y c liz a tio n o f 5 « * ( 1 ,2 ,5 . lO b rte t rah y d ro f lu o ra n th y l) - a c e t i c Aeid (IX ). Two grams o f th e a c id IX was e y e liz e d by th e same procedure used to e y c liz e ^ - ( 9 - f lu o r y l) - p r o p io n ic a e id . The p ro d u ct was r e e r y s ta lliz e d from a lc o h o l in s te a d o f b ein g d i s t i l l e d , A y ie ld o f 1 .1 g . (59$) o f 15 l f k e to - 1 , 2 , 2a , 3, 4, 4a-h ex ah y d ro e y c lo p e n ta (c d )flu o ra n th e n e (X) was o b ta in e d . The ketone was dim orphic, c r y s t a l l i z i n g in c o lo r le s s n e e d le s from a lc o h o l, which on sta n d in g o v e rn ig h t in co n ta c t w ith th e s o lu tio n , changed to hexagonal p l a t e s . B oth form s gave a m e ltin g p o in t o f 1 3 4 -5 °. A nal. C aled . f o r C-^gH^O: C, 8 7 .6 0 ; H, 5^73. Sbund: C, 8 7 .8 1 ; H, 5 .8 4 . The oxime, m .p . 192-3°, was p rep ared in p y rid in e s o lu tio n acco rd in g to th e pro ced u re d e sc rib e d by S h rin e r and Fuson23* Anal. C aled . f o r C 18H15N0s IT, 5 .3 6 . Found N, 5 .1 2 . Clemmensen R eduction o f l-K e to -l,2 .2 a ,3 .4 .4 a -h e x a h y d ro c y c lo p e n ta (c d )- flu o ra n th e n e (X ). The k eto n e X was reduced acco rd in g to th e procedure used by Bachmann and E dgerton 24 to reduce l t - m e th y l- 5 - k e to -5 ,6 ,7 ,8 -te tr a h y d ro - l, 2-b en zan - th ra c e n e . A m ix tu re o f 20 g ; o f amalgamated z in c , 24 m l. o f c o n c e n tra te d h y d ro c h lo ric a e id , 20 m l. o f g l a c i a l a c e tic a c id , 20 m l. o f to lu e n e and 2 .1 g . o f ketone was re flu x e d f o r f o r ty - e ig h t h o u rs. D uring t h i s tim e 20 m l. o f a c e tie a c id and 20 m l. o f c o n c e n tra te d h y d ro c h lo ric a c id were added in p o r t i o n s . The hydrocarbon o b ta in e d from th e to lu e n e la y e r was r e c r y s t a l l i z e d from a lc o h o l and a y ie ld o f 1 ,2 g . ( 6 0. 65 6) o f c o lo r le s s n e e d le s o f 1 , 2 , 2 a ,3 ,4 ,4 a -h e x ah y d ro e y clo p e n ta (cd )flu o ran th e n e (XI) was o b ta in e d . The compound m elted a t 92-3°, and when the m elted sample cooled and s o li d i f i e d i t m elted a t 8 2 -3 °• A n al. C aled . f o r Ci8Hi 6 : c > 93*0 6 » 6.94* Found: C, 9 2 ,7 5 ; H, 7 .0 7 , D ehydrogenation o f 1 .2 .2 a .5 .4 .4a-H exahydrocyclopenta(cd)flu o ra n th e n e (X I) . A m ix tu re o f 1 .3 g . o f th e hydrocarbon X I, and .065 g . o f p allad iu m on carbon c a ta ly s t was p la ce d in a t e s t tu b e . A ir was d isp la c e d by carbon d io x id e from a p e l l e t o f d ry ic e , and th e tu b e was slow ly h e a te d to 320°. E v o lu tio n o f hydrogen began a t 260°, At th e end o f o n e -h a lf hour th e 16 r e a c tio n was o v er and two m oles o f hydrogen p e r mole o f hydrocarbon had been evolved* The s o lid p ro d u ct was d iss o lv e d In benzene) broiled w ith ch arco al and passed th ro u g h an alum ina column* A fte r rem oval o f th e benzene, th e product was r e e r y s ta lliz e d from a lc o h o l and acetone to y ie ld 0 .7 g* o f p a le yellow n e e d le s, m .p. 152*4 * A second crop ( .3 g . ) had a m.p* o f 151*3°* The t o t a l y ie ld was 1 g* (78$) o f 1 , 2 -d ih y d ro c y c lo p e n ta- (e d )flu o ra n th e n e (V ). Two r e c r y s t a l l i z a t i o n s r a is e d th e m.p* to 1 5 4 -5 °; A n al* Caled* f o r 6 -^gH^gs 0) 94«75{ H, 5*25* Founds C, 94*92j 5*07* P re p a ra tio n o f E th y l 3 -F lu c sran th y la c e ta te (X7) ♦ A m ix tu re o f 2 g . o f th e mixed e s te r s from th e Beform atsky B eaetio n a n d .l g* o f p allad iu m on carbon c a ta ly s t was p la c e d in a t e s t tube* The system was flo o d ed w ith carbon d io x id e from a p e l l e t o f d ry ic e , and slo w ly h e a te d up to 280-90° in a Wood's m etal bath* At th e end o f one hour and f if t e e n m in u tes s l i g h t l y more th a n th e t h e o r e tic a l volume o f hydrogen had been evolved* The t e s t tube was cooled and th e product was r e e r y s ta lliz e d from alco h o l* A y ie ld o f 1 .8 g* (90$) o f e th y l 3 - f lu o r a n th y la c e ta te (X7), m .p. 109-12°, was o b ta in e d . A mixed m eltin g p o in t d e term in a tio n w ith th e e s te r is o la te d from th e B eform atsky B ea etio n showed no depression* S a p o n ific a tio n o f E th y l 3 -g lu o ra n th y la c e ta te (X 7)» A m ix tu re o f 1 4 .8 g . o f e th y l 3 - flu o r a n th y la c e ta te (X7) and 150 ml* o f 20$ potassium hydroxide was b o ile d f o r tw en ty m in u te s. The a c id was p r e c ip ita te d by th e a d d itio n o f h y d ro c h lo ric a c id , f i l t e r e d , d rie d and r e e r y s ta lliz e d from g l a c i a l a c e tic acid* A y ie ld o f 1 1 .5 g* (86$) o f 3 -flu o x a n th y la c e tie a c id c r y s ta lliz e d in p a le yellow p la te s from a c e tic a c id , m .p; 233*4°, Anal* Caled* f o r C^gH^gOg: C * 63*07; H, 4*65* Found: C* 82*92; H, 4.74 A ttem pted C y c liz a tio n o f 3 -F lu o ra n th y la e e tie A cid* Two grams o f 3 - f lu o r a n th y la c e tic a c id was h eated w ith 2 m l. o f th io n y l c h lo rid e f o r tw en ty m in u tes on th e steam hath* The e x cess th io n y l c h lo rid e was d i s t i l l e d o f f under reduced p ressu re* th e a c id c h lo rid e was d iss o lv e d in 15 ml* o f n itrobenzene* and slo w ly added to an ic e -c o ld s o lu tio n o f 2 g . o f aluminum e h lo rid e in 16 m l; o f n itro b en zen e* The m ix tu re was m ain tain ed a t 0° f o r f o u r hours* and h y d ro ly sed by p o u rin g o nto a m ix tu re o f ic e and h y d ro c h lo ric acid * The n itro b e n z e n e la y e r s o li d i f i e d im m ediately upon h y d ro ly sis* Steam d i s t i l l a t i o n l e f t 1*6 g* o f a yellow powder* in so lu b le in b o ilin g nitrobenzene* p y rid in e* dioxane* a c e tic acid* and acetone* When h ea te d to 340° th e powder d id n o t m elt* b u t darkened a t 300°; Summary ^ - F lu o r y lp r o p io n ic a c id h a s been p rep ared by th e M ichael Condensa tio n o f 9 -c arb e th o x y flu o re n e w ith a e r y l o n i t r i l e , fo llo w ed by s a p o n ific a tio n The hydrocarbon, 1, 2-d ih y d ro e y e lo p e n ta { c d )flu o ra n th e n e has been sy n th e siz e d b y th e fo llo w in g sequence: 3 - k e t o - l , 2, 3 , lO b -te tra h y d ro flu o r an th en e was caused to undergo th e Re fo m a t sky R ea ctio n w ith e th y l bromo- a c e ta te , to form e th y l 3 - ( 1 ,2 ,3 ,lO b -te tra h y d ro flu o ra n th y l!d e n e )-a c e ta te , which was th en s a p o n ifie d to form 3 - ( l , 2 ,3 ,lO b -te tra h y d ro flu o ra n th y lid e n e ) - a c e tie a c id ; t h i s a c id was hydrogenated to f o m 3 - ( l , 2 , 3 ,lO b -te tra h y d jo flu o r an th y l} - a c e t i c a c id , F r ie d e l C ra fts in tra m o le c u la r a c y la tio n o f which r e s u lte d in th e fo rm atio n o f l-k e to -l,2 ,2 a ,3 ,4 ,4 a -h e x a h y d ro c y c lo p e n ta (c d )- flu o ra n th e n e ; Clemmensen R eduction o f t h i s ketone r e s u lte d in th e forma tio n o f 1 ,2 ,2 a ,3 ,4 ,4 a-h e x a h y d ro c y c lo p e n ta (c d )flu o ra n th e n e , which y ie ld e d 1 , 2-d ih y d ro e y c lo p e n ta (c d )flu o ra n th e n e by dehy d ro g en atio n , 1 , 2-D ih y d ro c y c lo p en ta (e d )flu o ran th en e c o n ta in s two five-m em bered r in g s fu sed to th e o p p o site p e r i p o s itio n s o f th e n ap h th alen e nucleus* T h is i s th e f i r s t tim e such a r in g system h as been formed by c lo sin g th e second five-m em bered r in g by th e P rie d e l C ra fts in tra m o le c u la r a c y la tio n re a c tio n * A com parison o f th e u l t r a v i o l e t a b so rp tio n spectrum o f 1 ,2 -d ih y d ro - c y d o p e n ta (e d )flu o ra n th e n e w ith t h a t o f flu o ra n th e n e was made, and showed a g e n e ra l s im ila r ity , b u t w ith a s li g h t s h i f t tow ard th e v i s i b l e re g io n in th e case o f th e form er hydrocarbon* and d ecarb o x y latio n o f 9 -c a rb e th o x y -9 - -e y a n o e th y l)-flu o re n e * 1 z 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 B ib lio g ra p h y Mayer and Kaufraann, Ber## 53# 289 (1920)* F le is c h e r and Wolff* B ar.# 53* 925 (1920)« F ie s e r and P e te r s , J# Am. Chom. S o c ., 54, 4347 (1932) • S c h o ll and B o ttg a r, Bar** 63* 2128 (1930)# O lar, B a r;, 64B* 2194 (1931)* Fedorov, B ull# A cad. Sci# U .R .S .S .* C lasse S c i. ®hem., 1947# 397. D u fra isse and G ira rd , B u ll# S oc. Chisu* ( 5 ), 1,1359 (1 9 3 4 ). B u fra iss e , B u ll. S oc. Chim#* ( 5 ) , 3, 1857 (1 9 3 6 ). Bachmann and K lo e tz e l, J* Am. Cheat* Soc.* 59, 2207 (1 9 3 7 ). Ton Braun and Anton, B ar.* 62B, 145 (1 9 2 9 ). Franca* M aitlan d and T ucker, J# Chem. Soc.* 1937#-1739# F ran ce, T ucker and J b r r e s t, J . Cham. S o c ., 1945, 7 * F o rre s t and T ucker, J . Chant; S o c ., 1948, 1137. T ay lo r and Connor, J . Org. Cham.* 6* 696 (1 9 4 1 ). P in c k and H ilb e r t, J . Am; Chem* S o c ., 68, 2014 (1946). B ruson, J# Am; Chem. S o c ., 64* 2457 (1 9 4 2 ). Bachmann and Edgerton* J . Am. Chem. S o c * 62, 2971 (1940)# Robertson* P ro c . Roy. S o c ., A142, 674 (1 9 3 3 ). German P a te n t 230* 237, O ct. 23* 1909. O rchin and Reggel* J . Am # Chem. Soc.* 69, 505 (1947). Hurd and Mold* J . O rg. Chem.* 13* 330 (1 9 4 8 ). A dickes, J • P r a k t. Chem.* 143* 345 (1936)* S h rin e r and Fuson, I d e n tif ic a tio n o f O rganic Compounds, 2nd Ed.* 167. Bachmann and Edgerton* J . Am. Chem. Soc.* 62* 2550 (1940). OltfWfefbr of Southern California

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Creator Chubb, Francis Learmonth (author)

Core Title The synthesis of 1,2-dihydrocyclopenta (cd) fluoranthene

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Degree Master of Science

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Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-791230

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